This document is the preface to Volume 4 of Chemistry and Technology of Explosives by Tadeus Urbanski. It provides background on the scope and contents of the volume, acknowledges those who contributed information and assistance, and thanks the various organizations that granted permission to reuse content. The preface expresses the author's dedication to peaceful applications of explosives and avoidance of military topics. It aims to comprehensively but critically cover available literature on the subject as of the late 1980s/early 1990s.

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Chemistry and Technology
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VOLUME 4
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5. .J I.
:l~
Chemistry and Technology
of Explosives
Volume 4
by
TADEUSZ URBANSKI
Institute ofOrganic Chemistry and Technology,
TechniCilI University (Politechnika), Warsaw, Poland
PERGAMON PRESS
Member of Maxwell Macmillan Pergamon Publishing Corporation
O~FORD . NEW YORK· BEIJING' FRANKFURT
SAO PAULO· SYDNEY, TOKYO· TORONTO

6. U.K.
U.S.A.
PEOPLE'S REPUBLIC
OF CHINA
FEDERAL REPUBLIC
OFOERMANY
BRAZIL
AUSTRALIA
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CANADA
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CoPyrilht @ 1964 Palstwowe Wydawnictwo Naukowe,
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All Rights Re:serv«l. No fHlrt 0/ this pllblicatlon "'Dy be
nprodlle«l, stored In Dntrle"DI syste", or trDIIS",ltt«l in
Dny /or", or by Dny ",HIIS: electronic, electrostDllc,
mDgnetic tDpe, mechDnlca/. photocopying. recording or
otherwise. withollt permission in writing from the copyright
holders.
First Enllish edition 1964
Reprinted (with corrections) 1983
R~printed 1988,1990
1..1.....'1 of e•....- e.I......... I. PlIbHall_ o.ta
(Revi5Cd for vol. 4)
Urbalski. Tadeusl.
Chemistry and technology of explosives.
Translation of: Chemia i technologia material6w
wybuchowych.
Vol. 3 translated by Marian Jurecki. edited by Sylvia
Laverton.
Includes bibliographies and indexes.
I. Explosives. I. Laverton. Sylvia. II. Title
TP270.U713 1965 662'.2 ·83-2261
Brit'" Uhnry e........I.. I. PlIbIIaI_ Del.
Urbalski. T.
Chemistry and technology of explosives.
Vol. 4
1. Explosives
I. Title
662'.2 TP270
ISBN 0-08-026206-6
Print«l in arHt SritDin by
Antony Ro~ Ltd, ChlppenhD"', Wiltshlrr

7. PREFACE
Since 1964-67 when the previous three volumes of Chemistry and Technology
ofExplosives appeared, considerable progress has been made in the field ofthe
science of explosives - the science in a broader sense which includes not only
the theoretical knowledge of explosives but also their manufacture, problems of
safety in the manufacturing processes and handling.
AI in the previous three volumes the author limited his text to chemistry and
technology of explosives. The problems of the theory of detonation and analyti-
cal ones are not discussed here and are only touched as much as it was needed to
understand the properties of explosives. Thus in the 'Introduction' chapter a
description is given of the relationship between the chemical structure and the
parameters of the explosive properties, as this refers to the structural problems
of organic substances possessing such properties.
However, the author wishes to point out that he is not giving the full review
of the existing progress for some particular reasons - a general philosophy for
Peace in the World and some personal reason as a former POW. He is completely
against the use of explosives for military purposes and has dedicated his book to
peaceful applications.
The author wishes to quote from the book by S. Fordham, High Explosives
and Propel1Jznts (pergamon Press): "The explosives technologist, who has usually
seen and perhaps even experienced the effects of explosives is the last to want
war or for his products to be used for warlike purposes. It is no accident that
Nobel who founded the modem explosives industry also founded the Peace Prize
associated with his name".
Once more the author would like to repeat what he said in the preface to his
book in 1964-67: ..... more explosives have been used in peace than in war.
Modem civilization and modem progress would be impossible without explos-
ives." Nevertheless, following this line of thought no mention is made in this
book on shells, projectiles, fuses etc., or other parts of military weapons. How-
ever it is still difficult to distinguish between military and peaceful application of
military weapons. Here are a few examples:
Gas bUrning from a newly drilled oil pit in Karlin in Northern Poland in
1981 was successfully extinguished with howitzer shells; the danger of an
avalanche of snow can be prevented by firing special guns with shells filled
v

8. vi PREFACE
with high explosives; firing rockets with explosives loaded with silver
iodide is in use for promoting rain (Vol. III, p. 324). Silver iodide dis·
persed in higher layers of atmosphere by anti-aircraft rounds is in use in
the U.S.S.R., according to "TWA Ambaswlor" (p. 37, May 1981).
A conscientious attempt has been made to cover the available literature on
the subject, however not every paper and report has been mentioned as it was
considered to be of greater value to couple a reasonably comprehensive coverage
with a critical assessment of the available information and not to describe every
paper. The excellent Encyclopedill of Explosives and related items produced by
(the late) B. T. Fedoroff, O. E. Sheffield and S. M. Kaye should be consulted for
the whole literature on explosives.
Also excellent reviews have appeared in Volumes of An1UUl/ Reviews of
Applied Chemistry, Issued by Society of Chemical Industry, London, between
1950 and 1975, written by J. Taylor, E. Whitworth, W. E. Batty, I. Dunstan and
a number of authors from I.C.I. Ltd.
The author apologises to the authors for any important work overlooked in
the present volume.
It is the pleasant duty of the author to thank an the colleagues who res-
ponded to his request for information. I am most grateful to them. They were
from:
(1) Federal Republic of Germany: Dr A. Homburg (Koln), Dr R. Meyer
(Essen), Dipl. Ing. H. Plinke (Bad Homburg), Dr H. Schubert and Dr
Fred Yolk (Pfmgstal).
(2) France: Ingenieur A. Delpuech (Sevran), Ing6nieur G6n6ral P. Tavernier
(Paris).
(3) Holland: Professor Th. J. de Boer (Amsterdam).
(4) India: Dr A. K. Chatterjee (Hyderabad) and Dr S. P. Panda (Poona).
(5) Japan: Mr K. Yamamoto (Asa), Professor T. Yoshida (Tokyo).
(6) Italy: Dr E. Camera (Udine).
(7) Sweden: Dr Jan Hansson (Sundbyberg), Dr G. A. Wetterholm (Gote-
borg). .
(8) Switzerland: Mr GUido Biazzi, Dr G. S. Biasutti and Dr A. Fauci (Vevey).
(9) U.K.: Mr A. Brewin, M.A. (ERDE, Waltham Abbey).
(10) U.S.A.: Professor J. F. Dunnett (Santa Cruz, Cal. ), Mr C. L. Coon (Uver-
more, Cal.), Professor J. A. Concling (Chestertown, Md.), Professor
H. Feuer (Lafayette, Ind.), Dr Mortimer J. Kamlet (Silver Spring, Md.),
Professor Nathan Kornblum (Lafayette, Ind.), Dr A. T. Nielsen (China
Lake, Cal.), Professor G. A. Olah (Los Angeles, Cal.), Professor Glen A.
Russell (Ames, Iowa), Dr R. W. Van Dolah (Pittsburgh, Pal, S.M. Kaye
(Dover, New Jersey).
(11) U.S.S.R. (Moscow): particularly to the late Professors K. K. Andreev and
S. S. Novikov, Professors V. I. Pepekin and V. V. Sevostyanova and

9. PREFACE vii
Dr G. T. Afanasyev, Dr G. N. Bezpalov, Professor V. K. Bobolev, Pro·
fessors L. V. Dubnov and A. P. Glazkova, Dr B. N. Kondrikov, Professor
V. V. Perekalin (Leningrad).
(12) Poland: the late Professor W. Cybulski/Miko16w/, Dr T. Krasiejko,
Dr R. Kuboszek, Dr K. Lewanska, Dr T. Mrzewiliski, Dr M. Parulska,
Dr W. Sas, Professor M. Witanowski and Mr M. Zi6lko - all from War-
saw, and the Directors of the Institute of Organic Industry, Warsaw:
Prof. S. Fulde, Dr W. MoszczyDski and Mrs J. Zoledziowska for their
assistance.
My thanks are due to Dr R. Kuboszek for his help in the proof reading and
preparing the subjects index.
The author thanks industrial firms which supplied him with most valuable
information on their processes and apparatus. They are: Dr Ing. Mario Biazzi
S.A., CH-1800 Vevey, Switzerland; Bofors Nobel Chematur, S-69020 Bofors,
Sweden; Draiswerke Maschinenfabrik G.m.b.H., Mannheim-Wahldorf, Dynamit
Nobel A.G., D-5000 Koln, Jenaer Glasswerk, Schott u.Gen., 0.6500 Mainz, in
FRG; Kemira OY, Vihtavuori, Finland; Maschinenfabrik Fr. Niepmann G.m.b.H.,
D-5520 Gevelsberg, Westfalen FRG;Nitro-Nobel A.B., S-7103 Gyttorp, Sweden;
Adolf Plinke Sohne, 0.638 Bad Homburg, Wasag Chernie Sythen G.m.b.H.
1).4358 Haltern, Westfalen, and Werner & Pfleiderer, 0-7000 Stuttgart, FRG;
Nippon Kayaku Co. Ltd, Asa, Japan; S.A.PRB-Nobel-Explosifs, B-1960, Sterre-
beck, Belgium; U.S. Bureau of Mines (Washington D.C.); IOL Chemicals Ltd,
Hyderabad, India.
The author is also grateful for the permissions received to reproduce the pic-
tures, diagrams and text from books and journals published by:
1. American Chemical Society,
2. Department of Defence, Dover, N.J., U.S.A.,
3. John Wiley and Sons, Inc., New York,
4. Plenum Press, New York,
S. Verlag Chernie, Weinheim, FRG.
Finally my thanks are due to Mr I. Robert Maxwell, M.C., Chairman of
Pergamon Press Ltd, Oxford, Mr Alan J. Steel, Publishing Director, Dr Colin J.
Drayton, Senior Managing Editor and Mr Peter A. Henn, Senior Publishing
Manager of Pergamon Press, and Mrs Eileen Morrell for tidying up my 'foreign'
English.

10. CONTENTS
Introduction
Novel information on explosive properties
Calculation of detonation properties
Sensitivity of explosives to impact
Action of ultrasonic waves and luer pulse
Action of irradiation
Influence of high temperature
Increasing the strength of explosives by adding metals
References
Chapter 1. Nitration and nitrating agents
Nitric acid
Nitric and sulphuric acid
Effects of adding salts on nitration in sulphuric acid
Nitric acid and triOuoromethane suiphonic acid
Nitric acid and hydroOuoric acid
Nitric acid and phosphoric acid
Nitric acid and acetic anhydride
Nitric acid with cerium ammonium nitrate or tallium nitrate
Nitronium cation (NOi) and its salts
Dinitrogen pentoxide
Dinitrogen tetroxide and nitrogen dioxide
Dinitrogen tetroxide, nitric acid
Friedel-Crafts nitrating agents
Solid superacid catalysts
Alkyl nitrates and boron trifluoride
Nitric acid and mercury salts
Inorganic nitrate salts and trifluoroacetic acid
Nitrous acid
Nitrosyl chloride
Nitrate esters in alkaline medium
Aliphatic nitro compounds
Nitroamines
References
Chapter 2. Nitration ofaromatic systems
IDfluence of substituents on nitration
Ipso-nitration
Aromatic radical cation
Reversibility of aromatic nitration
ix
1
2
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48
SO
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11. x CONTENTS
Nitration wader the iafluence ofgamma radiation
Iodirect methods ofintroduciDg a nitro group
Substitutionof sulphonic group
Substitution ofdiazo group
Substitutionof halogen
SubstitutionofI-butyl group
Introducing the nitro group by oxidation
Oxidation of primary amino group
Oxidation ofoximes
Diffusion control in nitration
Influence of a positively charged substituent
Side reactions
References
Chapter 3. Structures and pbysicOo<bemical properties of
nitro compounds
Electronic spectra ofthe nitro groups
Solvent effect
Infra-red and raman spectroscopy
Nuclear magnetic resonancc ofnitro compounds
Proton magnetic resonaucc
Nitrogen magnetic resonance
Electron spin resonance
Micro-wave spectroscopy
Magnetic and electric birefringancc
Optical rotatory dispersion
Hydrogen bond with the nitro groups
Charge-transfer complexes (cr-(:Omplexes) or electron-donor-acxeptor
complexes (EOA-Complexes)
X-Ray structure
Thermochemistry
Mass spectrography
Electrochemical Properties
Galvanic cells .
Biological activity of nitro compounds
References
Chapter 4. Reactivity ofaromatic nitro compounds
Substitution (heterolytic and homolytic)
Electropbilksubstitution
Nucleophilic addition and substitution
Nucleopbilic displacement ofnitro groups
Jackson-Meisenheimer reaction and complexes
Practical significance and application ofJackson-Meisenheimer reaction
Reaction potential map (RPM)
MyceUar nucleophilic reactions
JlUlOVSky reaction
Action ofbases in nucleophilic reactions of nitro compounds
Action of Grignard reagent on nitro compounds
RcIaion ofaromatic nitrocompounds with diazomethaue
57
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60
60
60
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69
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CJ7
CJ7
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101
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103
104
107
109

12. CONTENTS xi
Mechanism of Richter reaction 109
NQCleopbilic substitution in gas phase 110
~nsofnKticUioDS 110
RadicU anions of nitro compounds 110
Free radical reactions 112
Action ofaromatic nitro compounds on polymerization 115
Reduction ofaromatic nitro compounds 115
Formation ofnitroso compounds 115
Reduction of aromatic ring 116
Diazotization of mno nitro compounds 118
l,3-Cycloaddition of nitro compounds 119
1bermal stability of aromatic nitro compounds 120
Free radicals 121
Furoxancs 122
References 122
Chapter 5. Photocbemistry ofnitro compounds 129
Aliphatic and alicyclic nitro compounds 132
Photoconductivity of nitro compounds 133
Photolysis 134
References 135
Chapter 6. Nitro derivatives of benzene, toluene and other aromatics 138
Nitration of benzene to nitrobenzene 138
Nitrobenzene 139
m-Dinitrobenzene 139
ElectrochemicU propenies 140
Isomericdinitrobenzenes 140
sym·Trinitrobenzene 140
1.2,3,5-Tetranitrobenzene 141
1.2.4,5-Tetranitrobenzene 142
1,2,3,4-Tetranitrobenzene 142
Pentanitrobenzene 142
Hexanitrobenzene (HNB) 143
Other high nitrated derivatives of benzene obtained by the method of Nielsen 143
Nitro derivatives of toluene 144
Nitration oftoluene to nitrotoluenes 144
Mononitrotoluenes 145
Industrial methods of mono-nitration of benzene and toluene 145
Removal ofphenolic by-products 146
Periodic nitration 146
Continuous nitration 146
Soviet method (according to Chekalin, Passet and toffe) 147
Bofors·Nobel·Chemarur method of nitrating benzene and toluene to
mononitro products 150
Dinitrotoluenes 151
Physical (including thermochemical and explosive) propenies 152
Formation ofdinitrotoluenes from mononitrotoluenes 153
Industrial methods ofdinitracion of benzene and toluene 154
Modernized pilot-plant and industrial production of DNT 154
Low temperature nitration oftoluene to DNT 154
Bofors-Nobel-Chematur method ofmanufacture of DNT 156

13. xii CONTENTS
BiazziS.A., Veveycontinuousmethod 157
T~~~~~ 1~
Physical (including thermochemical and explosive) properties 1~
Chemical properties of2,4,6-trinitrotolue~ 164
Reaction with sodium sulphite 164
Oxidation of 2,4,6-trinitrotoluene 165
Reduction of 2,4,6-trinitrotoluene 165
Methylation of2.4,6-trinitrotoluene 166
Ulllymmetrical isomers of trinitrotoluene and by-products of nitration of toluene 166
Tetranitromethane 168
White compound 169
Impurities ofTNT 171
Sulphitation of crude TNT ('scllite' process) 172
By-products formed in the course of purification ofTNT with sodium sulphite 173
Utilization of dinitrosulphonic acids formed in scllite process 173
Pentanitrotoluene 175
TNT Manufacture 176
Bofors-Chematurcontinuous method 177
Low temperature process for TNT manufacture 178
Manufacture of TNTin the U.S.A. during World War II 181
One-stage Nitration oftoluene 181
Two-stage process ofnitration 182
Three-stage process 182
Direct nitration process 182
Purification ofcrude TNT 185
Soda-ash process 186
Ammoniacal scllite process 186
Alkaline scllite method 187
Safety of manufacture and handling of aromatic nitro compounds, particularly of
benzene and toluene 187
Environmental problems ofTNT manufacture 190
Other nitroaromatics 190
Nitro derivatives of hydrocarbons 190
Nitro derivatives of halogenohydrocarbons 191
Nitrophenols 191
~cricacid 191
Salts of picric acid 192
2,4-Dinitroresorcinol 192
Purification 193
Styphnic acid 193
Tetranitrodian 193
~cric acid ethers 194
Hexanitrodiphenylamine (hexyl) 195
~cramic acid 195
Other aromatic nitro compounds with amino groups 195
References 195
Appendix 1 199
Derivatives of halogeno.benzene 199
Appendix 2 201
ADalysis of nitrating acids 201
Appendix 3 201
Chapter 7. Heat resistant explosives 202
Nitro derivatives of benzene 203
Ni~ derivatives of diphenyl 205

14. CONTENTS
Nitro derivatives of bibenzyl and stilbene
Nitro derivatives of bibenzyl
Nitro derivatives ofstilbene
Nitro derivatives of aromatic aza pentalenes
Nona· .
Potential heat resistant explosives
Resistance to irradiation
References
Appendix
Chapter 8. Aliphatic nitro compounds
Mononitro alkanes
Other methods of introducing the nitro group into saturated compounds
Oxidation of amines
Reaction of alkyl halides with sodium nitrite
Nitromercuration of a1kenes
Formation of nitroalkanes from nitrate esters
Qaemical properties of nitroalkanes
Nitronic acids
Polar solvents favour the aci-form
Activating influence of the nitro group
Nitromethane
Nitroethane, I-nitropropane and 2-nitropropane
Arylnitroalkanes
Nitrocycloalkanes
Esters of nitroalcohol and unsaturated acids
Industrial methods of nitrating alkanes
German method ofnitration of lower alkanes
Method of Commercial Solvents Corporation, Inco
Distillation
Hazards of the nitration of alkanes
1,2-Dinitroethane
2,2-Dinitropropane
Nitroalkenes
Methods ofpreparation of nitroalkenes
Recent reactions of formation ofnitroalkenes
Chemical propenies of nitroalkanes
Addition reactions
Isomerization
°R.eduction ofthe double bond
Polymerization
Nitroacetylenes
Polynitro aliphatic compounds
Nitration of hydrocarbons
Substitution of halogen
Electrolytic methods
Addition reaction
Michael addition
Diels-Alder addition
Oxidative dimerization
a, CIl-Dinitroalkanes
gem-Dinitroalkanes
Trinitromethane (nitroform) derivatives
Propenies of nitroform
Manufacture of nitroform
xiii
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206
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211
213
213
215
215
217
218
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219
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220
221
221
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240
240
241
241
242
242
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245
246
248

15. xiv CONTENTS
TelraDitrometbane (TNM) 251
Physical and pbysieo<bemical properties ofTNM 251
Chemical properties 252
Nudeopbilic substitution 253
Nitrosation of tertiary &mines 253
aem-Dinitromethylation 253
Nitration 2S4
Radical reactioDS 25S
Ionic polymerization 25S
Metalorpnic compounds 255
Explosive properties 25S
Th~~ ~
Preparation ofTNM 256
Hexanitroethane (HNE) ~
Nitrocarboxylic acids 257
Nitrodiazomethanes 258
Nitro derivatives of urea 259
N,N-bis(P,P,P)-trinitroethyl urea 2S9
Nitroso compounds 25'
Nitro-nitroso alkanes ('Pseudonitroles') 259
'Hexanitrozobenzene' 260
Nitroenamines 260
References 261
Appendix 268
References 269
Chapter9. DIfIuoroamiDocompounds 270
Direct Duorination ofnon-aromaticcompounds 270
Directfluorination ofNH:zand NH groupsinaliphaticcompounds 271
Ditluoroamine (difluorimide) NHF2 271
Other non-aromatic difluoroamines 2n
F1uorination ofnitroaromatic amines 273
I-DiOuoroamino-2,4-dinitrobenzcne 273
Other difluoramino nitroaromatics 275
F1uorination throup the addition oftetraOuorohydrazine 275
Tetrafluorohydrlizine NF2-NF2 275
Reaetivi~ oftetraOuorohydrazine 276
Explosive ~perties ofdifluoroaminoalkanes and alkenes 277
Theoretical aspectsofpropeniesofNF:zcompounds 278
Thermochemistry 279
References 279
Chapter10. Esters 281
Nitrate esters (O-nitrocompounds) 281
Structure 281
~pokmomen~ 281
Spectroscopy 282
Nuclearmagnetic resonance 284
Electronattractingpropertiesofnitrate esten and charge-transfercomplexes 284
Hydrolysisofnitrate esten 1Jr1
Reductionofnitrateesten 289
Conversionofnitrate esten into nitroalltanes 289

16. CONTENTS
Formationofnitrate esten
Gas-cbromarographyofalkylnitrates
Alkenesu asourceofnitrate esten
Nitrate estenu explosives
Biologicalaction ofnitrate esten
Glycerol tJ'initrate (nitroglycerine)
Settingpoint
Vapourpressure
Absorptionspectra
Olemicalproperties andstability
Sensitivityto impact
Burningofnitroglycerine
Explosion and Detonation ofnitroglycerine
Glyceroldinitrates ('dinitroglycerine') and derivatives
Glycerol-nitrolaetate dinitrate
Glycerol2,4-dinitrophenylether andtrinitrophenyletherdinitrates
Hexanitrodiphenylglycerol mononitrate
Mixedestenofglycerol
Glycol nitrates
Ethylene glycol mononitrate
Ethylene glycoldinitrate
Diethylene glycol dinitrate
Triethylene glycol dinitrate
Butine-2-diol-l,4dinitrate
Nitrate estenofmonohydroxylic alcohols
Methyl nitrate
Ethyl nitrate
,.-Propyl nitrate
iso-Propyl nitrate
Polyhydroxylic alcohol esten
Butane-l,2,3-triol trinitrate
Erythritol tetranitrate
Pentitol pentanitrates
o-Mannitolpentanitrate
o-Mannitol hexanitrate
Dulcitol 0- or L-galactitol hexanitrate and o-sorbitol hexanitrate
Pentaerythritol tetranitrate (PETN)
Thennodynamicproperties and thennal decomposition ofPETN
Explosiveproperties
Nitrationofpentaerythritol
Mixedpentaerythritol andglycerol esten
Methodsofpreparation ofPETriN and PEON
Nitrite csten (O-Nitroso Compounds)
Eaten ofoxy-acidsofchlorine
Geminal diperchlorates
References
Appendix
N-oxidcs
Chapter 11. Productionornitrateesters
Nitroglycerine (NG)
Hercules tubular process
Biazziprocess
Control ofthe nitration
xv
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29S
29S
29S
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30S
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17. xvi CONTENTS
SeparationofNG from the spent acid 328
Alkaline washingofNG 328
Tcc:hnical data ofBiazzimethod 328
Safetymeasures 329
Injeaor nitration process 330
Safetyproblems 331
Diethylene glycol dinitrate (DGDN) 332
Tricthylene glycol dinitrate 333
Manufactureofpentaerythritol tetranitrate (PETN) 333
PurificationofPETN 336
References 338
Chapter 12. Carbobydrate nitrates 339
CcUulose and cellulose nitrates (nitrocellulose) 339
CcUulose for nitration 339
Structure ofcellulose polymer and determinationof molecularweight 340
Pyrolysisof nitrocellulose 341
Thermochemicalproperties ofnitrocellulose 341
Mixed esters: nitratesandsulphates 342
Stabilizationofnitrocellulose 343
Kn«ht compound 345
Manufacture of nitrocellulose 345
Semi-continuous method ofBofon-Nobel-Chematur 345
Dryingofnitrocellulose 348
Safetyin the manufactureofnitrocellulose 349
Starch nitrates (nitrostarch) 349
Nitratesofvariouscarbohydrates 350
Polyvinyl nitrate 351
Nitro-derivatives oflignin 351
References 351
Chapter 13. N-Nltro compounds (N-nitraminesand N-nitnunides) 354
Structure and chemical properties 354
Preparationofnitramines 361
Formation ofdinitramines from nitroguanidine 361
N-Nitroenamines 361
Aliphatic nitramines and nitramides 361
Ethylenedinitramine (EDNA, Haleite) 362
Physical and chemicalproperties 363
Explosive properties 364
Nitroguanidine 36S
Reactions ofnitroguanidine 366
Specification according to Meyer 367
Nitroaminoguanidine 367
Nitrodiethanolamine dinitrate 368
Preparation 368
Dinitrodi·(~·hydroxyethyl)-oxamide dinitrate(NENO) 369
Aromatic nitramines 369
Tetryl 370
Heterocyclicnitramines 372
Cydonite (Hexogen, RDX) 372

18. CONTENTS
Structure
Spectroscopyofcyclonite
Chemicalproperties
Thermaldecomposition
Preparationofcyclonite
Preparationofcyclonitefrom hexamine dinitrate acetic anhydride
Explosive propertiesofcyclonite
MaDufaetureofcyclonite (RDX) according to Mario BiazziS.A. (Vevey)
Specificationfor cyclonite (Hexogen)
Disposalofwaste cyclonite
Toxicpropertiesofcyclonite
Explosiveswith cyclonite as amain component
Octogen
Structureand physical properties
Solubilityofoctogen
Cbemical properties
Thermal decomposition
Thermochemical and explosive propenies
Preparationofoctogen
Specificationfor octogen
Explosiveswith octogen as a main component
BSX(l,7-Diacetoxy-2,4,6-trinitro-2,4,6-triazaheptane)
Diagu and Sorguyl
N-Nitro-O-Nitrocompounds
References
Appendix
Chapter 14. Explosive polymers
C-Nitropolymers
Nitropolystyrene and its derivatives
Nitroindene polymer
Polynitroalkanes
Nitroethylene polymer
Polyurethaneswith aliphatic C- and N-nitro groups
Preparation
C-Nitropolymersfrom monomerswith a vinyl group
Nitroallyl acetate polymer
Ethylnitroacrylate
Nitroethylacrylate
Nitroethyl methacrylate
Trinitroethylacrylate
Dinitropropyl acrylate (DNPA)
Polyestersofdinitrocarboxylicacids and dinitrodiols
Polymerwith O-nitro groups
Polyvinyl nitrate (PVN)
PropertiesofPVN
Explosive properties
Preparation of polyvinyl nitrate
Practical useofpolyvinyl nitrate
Modificationsofpolyvinyl nitrate
Hydrazine anddiOuoroamine polymers
N·Nitropolymers
P1utic bondedexplosives
References
372
313
373
374
376
377
37g
379
380
381
381
381
382
383
387
387
388
390
391
393
394
395
396
3fJ1
3fJ1
402
404
404
404
404
404
404
405
409
411
411
411
412
412
412
412
413
413
413
413
414
415
418
419
419
420
420
420

19. CONTENTS
Chapter 15. Recovery ofspentadds 422
GeneraJ problemsofspent acidsfrom the nitration ofalcohols 422
Spent acidsfrom nitration ofglycerine 423
Stabilization ofspent acid 423
Denitration ofspent acid 423
Re-Uleofspent acid from the nitration ofglycerine 427
Spent acid ofPETN 429
Spent acid from cyclonite (RDX) manufacture 433
Spent acid from nitrocellulose 435
Spent acid from TNT 435
Spent acid from mononitrationoftoluene 435
Environmental problemsofdenitration 435
References 436
Chapter 16. Saltsofnitric acid and ofoxy-addsofchlorine 437
Ammonium nitrate 437
Hygroscopicityofammonium nitrate 439
Chemical and explosive properties 440
Hydrazine nitrates 441
Hydrazine mononitrate 441
Hydrazine dinitrate 442
Hydrazine nitrate complexes ('Hydrazinates') 443
Methylamine nitrate 443
Tetramethylammonium nitrate 443
Guanidine nitrate 444
Nitrates ofaromatic amines 444
Ammonium chlorate 444
Ammonium perchlorate 444
Crystal structure and physical properties 445
Thermaldecomposition and burningof AP 445
Thermal decompositionofirradiated ammonium perchlorate 447
Influence ofpressure on burningofAP 447
Density andcriticaldiameter 449
Decomposition (at higher temperatures) and burning ofammonium perchlorate
with various additives 449
Mechanism oflow-temperature decomposition ofAP 451
Explosive properties ofNH4 CI04 451
Manufacture of ammonium perchlorate 452
Specification 453
Perchlorate ofmetals 454
Other perchlorate 455
Hydrazine perchlorate 455
Hydrazine diperchlorate 455
Saltsofhydrazine perchlorate andchloratecomplexes 455
Nitrosyl perchlorate 456
Hydroxylamine perchlorate 456
Methylamine perchlorate 456
Guanidine perchlorate 456
Nitroguanidine perchlorate 456
Auoroammonium perchlorate 457
Nitronium perchlorate 457
Perchloric acid and chlorine oxides 457
Perchloricacid 458

20. CONTENTS xix
Olorine oxides 458
References 458
Chapter17. Primary explosives: initiators, initiating explosives(IE) 462
Introduction 462
BurningofIE under reduced pressure 463
Mercuricfulminate 464
Pbysical properties 46S
Chemical properties 466
Chemical stabilityand behaviour at high temperature 466
Behaviourat low temperature 467
Actionoflight 467
Burning under reduced pressure 468
Initiating propertiesofmercuric fulminate 468
Othersaltsoffulminic acid 469
Manufacture ofmercuricfulminate 469
Estersoffulminicacid 469
Hydrazoicacid, itsderivatives and salts 469
Dea>mposition ofazides 470
Heterocyclics from azides 470
Otber reactionsofazide anion and radical 471
Some organic azides 472
Dangerofbandling azides 473
Cyanic triazide 474
Explosive properties ofbydrazoicacid 474
Ammonium azide 474
Pbysico-chemical andexplosive properties ofmetal azides 475
Optical properties 476
Slowdecomposition ofazides 476
Fast decomposition and explosion 478
Lead azide 478
Propertiesoflead azide 479
Crystal structure ofa-Pb(N3h 479
Spontaneousexplosions ofazides 479
Sensitivity oflead azide 481
Stability and reactivity oflead azide 482
The manufacture oflead azide 482
Silverazide 484
Cadmium azide 486
Storage of azides 486
Toxicity 487
Destruction ofleadazide 487
Manufacture ofsodium azides 488
Sodium azide formation in liquidammonia 490
Tetrazene (Tetracene) 490
Tetrazole derivativesand theirsalts 492
Azotetrazole 493
Furoxane derivatives 494
Nitro derivativesofphenols 494
Lead mononitroresorcinol (LMNR) 494
Lead2.4-dinitroresorcinate 495
Basic lead 4,6-dinitroresorcinol 495
Lead styphnate 496
Leadsaltsofnitronaphthols 497

21. xx CONTENTS
ComplexsailS
1,3,5-Triazido-2.4,6-trinitrobcnzene
Dinitrobcnzenediazooxide (Dinitrodiazophenol, DDNP, DINOL)
Saltsofacetylene
Manufactureofprimers
Peroxides
Propione peroxide
Superoxides
References
Appendix
Chapter 18. Black powder (gun powder)
Modification of black powder
Explosive properties
Hygroscopicity of black powder
Manufacture of black powder
The use of black powder
Pyrotechnics
Accidents with black powder
History of black powder
References
Chapter 19. Commercial (Mining) Explosives
Introduction
Principles of composition of commercial explosives
Oxygen balance
Hygroscopicity of mining explosives
Stability ofcommercial explosives
Physical changes
Chemical changes
Rate of detonation and critical diameter
"Gap test" (Transmission of detonation)
Gap test and temperature
Channel effect
Possible spiral way and detonation of mixed explosives
Denagration of explosives in coal-mines
Evaluation of the strength of mining explosives
Safety against methane and coal-dust
Theory ofsafety against methane and coal·dust
Ammonium nitrate-fuel oil mixtures (AN-FO)
Explosive working of metals
Mining explosives used in various countries
Bulgaria
Germany
Great Britain
haly
Novel mining explosives used in Poland
Spain
Sweden
U.S.S.R. mining explosives
Permitted in sulphur mines and oil fields
Modern Japanese mining explosives
497
497
497
498
498
499
499
500
SOO
505
S06
508
510
511
511
513
513
513
513
513
515
515
515
515
517
519
519
519
520
520
522
522
523
524
525
527
529
530
532
532
532
532
533
534
535
538
538
538
542
542

22. CONTENTS xxi
Belgium 545
Water-gel (Slurry) explosives 546
History 546
Cross-linking agents 548
Surface active and emulsifying agents 548
Oxygen carriers 548
~~~m ~
Alkylamine nitrates 549
Gu bubbles 552
Permitted slurries 552
Slurries with high explosives 552
Composition of slurries with nitroglycerine based explosives 553
Nonel detonating fuse 554
References 554
Appendix 557
Methods of determining the ability of explosives to denagrate 557
Chapter 20. The manufaclure ofcommercial (mining) explosives 558
Planetary mixers 558
Canridging 561
AN-FO 562
References 567
Chapter 21. Liquid explosives 568
Liquid oxygen explosives (Oxyliquits. LOX) 568
Liquid rocket propellants-propergoles 568
Mono- and bipropellants 568
Cryogenic and storable components 569
Hypergolic systems 570
Novel trends in liquid rocket fuel 573
Oxidizers 574
Oxygen difluoride (OF2) 574
Nitrogen fluorides 574
Multicomponent fuel 574
Polymerization of hypergolic fuel 575
Analysis 575
References 576
Chapter 22. Smokeless powder 577
Stability of smokeless powder 577
Free radicals in the change of diphenylamine 581
Stabilizers 582
Kinetics of decomposition 584
Electric susceptibility of single base powder 584
Erosiveness of smokeless powder 585
Manufacture of powder 585
Single base powder 585
Double base powder 585
Traditional double base powder 585
Rocket double base powder 586

23. xxii CONTENTS
Cast propellants
Method ofmanufacture
Slurry-east propellants (Plastisol propellants)
Screw-extrusion process
Classical extrusion method
Higher energy smokeless propellants
References
Chapter 23. Composite propellants
Introduction
Polyurethane binders
Polybutadiene binders with carboxylic function
Hydroxytenninated polybutadiene binder (HTPB)
Curing butadiene polymers
Poly (vinyl chloride) plastisol propellants (PVC)
High energy composite propellants with HMX (Octogene)
Role of ingredients on properties ofcomposite propellants
Metals
Catalysts
Burning composite propellants containing ammonium perchlorate
Modifications ofcomposite propellants
Mechanical properties
Manufacture ofcomposite propellants
Shapes of the propellant grains
Explosive properties of composite propellants
References
Chapter 24. Problems of safety in the manufacture
and handling ofexplosives
Manufacture
Static electricity
Foreign bodies in mixing machines
Constructions ofexplosive factories
Detection of hidden explosives in luggage
Tagging of commercial explosives
General description of safety
References
Chapter 25. Toxicity ofexplosives
Aromatic nitro compounds
m-Dinitrobenzene
2,4·Dinitrotoluene
2,4.6-Trinitrotoluene
Aliphatic nitro compounds
2.Nitropropane
Tetranitromethane
Nitrate esters
Methyl nitrate
Nitroglycerine
587
587
588
590
596
596
599
602
602
604
605
609
609
611
613
613
614
614
615
616
617
617
618
618
620
621
621
622
623
623
623
625
626
626
627
627
627
627
628
628
628
628
628
628
629

25. CONTENTS
Nitrocellulose
Nitramines
Nitroguanidine
Cyclonite (RDX. Hexogene)
Octogene (HMX)
References
Subject Index
Contents ofprevious volumes, I, II, m
xxiii
629
629
629
629
629
630
631
649

27. INTRODUCTION
(Vol. I, p. 1)
NOVEL INFORMAnON ON EXPLOSIVE PROPERTIES
It has been shown that some non-explosive organic and inorganic substances can
explode when subjected to the action of very high pressure. 'This was recorded
for the fIrst time by Bridgman [1]. Teller [2] tried to fmd an explanation in
terms of the activation energy which should be lowered with increased pressure.
More recently Malmrud and Claesson [3] examined the behaviour of anum·
ber of compounds at a pressure of 35,000 kg/em2
• They found that some acids,
such as oxalic acid hydrate malonic, tartaric and citric acid, and other common
substances such as aspirin, sucrose, polystyrene and calcium chloride, exploded
when high pressure was released. A number of substances (e.g. succinic, glutaric,
adipic, maleic, fumaric, phthalic acids) did not show this behaviour. According
to the authors they did not explode because they required higher pressure.
The explanation given by Malmrud and Claesson is similar to that given by
Bridgman. They believe that over a critical pressure, which depends on the co-
efficient of friction, plastic flow stress and disc thickness, the sample becomes
mechanically unstable when pressure is released and is violently expelled.
Polystyrene was simultaneously carbonized which was probably caused by an
increased temperature due to heating by friction.
The author of the present book is inclined to rationalize that under very high
pressure considerable deformation ofthe crystal·net can occur and the atoms are
approaching distances which produce their repulsion.
The problem arises as to whether explosives can be brought to explosion by
high static pressure. So far the only published paper [4] indicated that nitro-
methane, perdeuteronitromethane and a few dinitroalkanes carmot explode at
static pressure up to 50 kbar.
It is known that acetylenic bond possesses endothermic characteristics (Vol.
III, p. 227) and it is interesting to point out that a number of acetylenic com·
pounds were found in nature as early as 1889 [5] and 1892 [6]. Currently
important are the works of E. R. H. Jones [7] and Bohlmarm [8] who isolated
and established the structure of numerous naturally occuiTing polyacetylenes
and confinned their structure by synthesis. Most of the polyacetylenes possess
explosive properties.

28. 2 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
Some hydroxylamine derivatives also show explosive properties. The simplest
of them is fulminic acid which can be regarded as an oxime of carbon monoxide
(Vol. III, p. 133). Lossen [9] has found that oxalohydroxamicacid(CONHOH)1
possesses explosive properties. Nitrogen sulphide N. S. - a formal analogue of
NO - possesses explosive properties. It explodes on heating to its m.p. 178°C or
on shock [78].
A surprising discovery was made in 1963 by several authors almost simul-
taneously and independently. This was that xenon trioxide possesses well
marked explosive properties. Thus N. Bartlett and Rao [10] while dissolving
xenon tetrafluoride in water, observed a vigorous reaction with the evolution of
hydrogen fluoride. Evaporation of the solution in vacuo at room temperature
left a white solid which exploded vigorously when warmed in vacuo above 30°
or 40°C.
D. F. Smith [11], Williamson and Koch [12] obtained the same compound
by hydrolysing xenon hexafluoride and mentioned its explosive properties and
described it as xenon trioxide. Templeton and co-workers [13] definitely estab-
lished by X-ray analysis that the white crystalline, non-volatile explosive was
xenon trioxide. It can best be prepared by hydrolysing xenon hexafluoride:
(l)
The explosive properties of the substance can be explained by the strongly
endothermic character of the substance [14]:
-M1r = -90 kcal/mol.
The search for novel ingredients of rocket fuels led to the discovery of new
groups producing explosive properties. One of them was the perchloryl group
(CI03 ), the compounds containing it are described in Vol. II, p. 488.
A new class of explosives which might possess some practical importance are
compounds of the difluoroamino group: NF1. Their first representatives were
obtained by Lawton and co-workers [IS] and Grakauskas [16]. A special
chapter (p. 270) is dedicated to this group of compounds.
CALCULA.;rION OF DETONATION PROPERTIES OF EXPLOSIVES
It is well known that the calculation of some constants, characterizing proper-
ties of explosives, starts from their decomposition equations. Such are: enthalpy
of decomposition and of formation, volume of gaseous products, their tem-
perature and so called specific pressure f. These constants are used extensively
to estimate the properties of high explosives (HE) and propellants. Other very
important constants of HE are: the velocity of detonation under given experi-
mental conditions or maximum velocity of detonation. Dmax , and pressure in
the front of the detonation wave.

29. INTRODUcnON 3
With the advent of the development of the hydrodynamic theory of deton-
ation, based on the concepts of Chapman [17] and Jouguet [18], it was possible
to calculate the velocity of detonation. The pioneering work was done by A.
Schmidt [19] and his method was improved by a number of autholl. Critical
reviews of the methods have been described in a number of monographs: Cook
[20], Zeldovich and Kompaneets [21], Andreev and Belyaev [22], Johansson
and Persson [23], Fickett and Davis [24].
The problems connected with the hydrodynamic theory of detonation are
outside the scope of this book and only papers dealing with the correlation
between the structure of explosives and their power will be given here. Originally
the papers were directed to correlate the oxygen balance (08) with the 'explos-
ive power'. This was initiated by Lothrop and Hendrick (Vol. I, p. 2) and met with
a well founded criticism (A. Schmidt, Vol. I, p. 2). The criticism was based on the
fact that oxygen in nitro groups has a different thermochemical function than
that of carboxylic and hydroxylic groups. The discussion aroused much interest
in the attempt to introduce a differentiation ofoxygen atoms.
The fust of the kind were papers by Martin and Yallop [25a, b]. They pro-
posed a 'corrected 08' calculated as follows:
08 =n =(z - 2x - y12) looln ± 100 win, (2)
where: x, y, z are the respective numbers of atoms of carbon, hydrogen and oxy-
gen in the molecule,
n - the number of atoms in the molecule,
w - summation of 0 atoms according to their linkages, thus:
w= 0 for oxygen atoms in NO] groups in C-nitro, O-nitro and N-nitro com·
pounds,
w = I for oxygen C-0 - NinO-nitro compounds,
w = 1.8 for oxygen C=0 in carboxylic groups,
w = 2.2 for oxygen in phenols and alcohols. ± Is taken: + if the first term is
+, and - if the first term is -.
The rate of detonation D was calculated from semiempirical equation (3)
[25aJ.
Dcak =2509 + 13.25 n + 3793 p + 12.81 p n (3)
where: p is the density of the explosive (gfcm3
).
In another equation they introduced the value H ca1/g of the heat of form-
ation [25bJ.
The work of Martin and Yallop was met with criticism. Thus Price [26J
concluded that 08 cannot determine the heat of explosion or detonation and
the rate of detonation cannot be a linear function of08. Roth [27J pointed out
that the correlation between Martin and Yallop's 'corrected 08' is successful
only for a restricted group of similar explosives. The correlation breaks down for

30. 4 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
explosives with a positive OB. He concluded that "OB is a concept that can pro-
vide useful qualitative infonnation. It should not be used for quantitative corre-
lation except ... for chemically similar explosives."
A number of authors: Qlowiak [28], Mustafa and lahran [29] and Pagowski
[30] tried to extend the method of Martin and Yallop. In particular Pagowsld's
work merits attention. He attempted to correct equation (2) of Martin and
Yallop suggesting the 'effective oxygen balance' B:
B =(z - 2% -l ±P) loo/n.
2
(4)
P is the correction accounting for energy gains or losses from the actual
chemical structure of the compound while taking into account different oxygen
atoms: those which are already bonded with carbon (C ==0, C-0 - N) and
those (N03 ) which are free to develop the exothennic reaction of oxidation.
For the rate of detonation Pagowski gave a semi-empirical equation (5):
D =8600 ±32.7 B (5)
at p = 1.6.
According to Pagowski the calculated values ofD fit well to experiments -
Table 1.
TABLE 1. Experimental and calculated values of D
Explosive
TNT
Tetryl
EDNA (1Il, 18)
Cyclonite (RDX)
PETN
Dexp
6980
7450
7920
8200
7820
Dealc
6345
7505
7900
8185
7880
Later a remarkable semi-empirical method of calculating the detonation press-
ure and velocity was given by Kamlet and co-workers [31].
Karnlet and Jacobs [31a] have shown that the detonation pressure and velo-
city, of C- H- N-0 explosives can be calculated at their initial densities above
1g/cm3
while using the following simple empirical equations:
P =15.58.p p3
D = 1.029.p (l +1.30 Po)3
(6)
(7)
(8)

31. INTRODUcnON 5
where:
P is the pressure in kbar,
D the detonation velocity in mIs,
N the number of moles of gaseous detonation products per gram of the
explosive,
M the average weight of these gases in g/mol,
Q the chemical energy of the detonation reaction (enthalpy -6HoIpg),
p = the initial density.
A few examples of the calculation of the velocity of detonation [2Sd] which
give an average error ofca. 1% only, are given in Table 2.
TABLE 2. Experimental and calculated rates of detonation
%
Explosive Dexp Dcalc deviation
(Dcalc-Dexp)
TNT 1.64 6950 6959 +0.1
1.445 6484 6395 -1.4
1.30 6040 5977 -1.0
1.00 5100 5111 +0.2
Picric acid 1.71 7350 7360 +0.1
1.25 6070 6000 -1.2
Ammonium picrate 1.55 6850 6798 -0.8
Tetryl 1.70 7560 7681 +1.6
EDNA (III, 18) 1.562 7750 7789 +0.5
RDX (CYclonite) 1.80 8754 8780 +0.3
1.60 8060 8098 +0.5
1.20 6750 6731 -0.3
HMX 1.90 9100 9117 +0.2
1.84 9124 8913 -2.3
1.77 8500 8671 +2.0
PETN 1.77 8600 8695 +1.1
A few examples of the calculation of Chapman-Jouguet pressure are given
below - Table 3 [31c]. The Kamlet method is very useful for the rapid calcu-
lation of most important constants characterizing high explosives.
Other remarkable methods of calculating parameters of detonation have been
developed by Pepekin, Lebedev and associates [32,33]. They worked out [32]
a method of calculation of heat of detonation when two factors are known: the
bulk formula of the explosive and the enthalpy of formation Mtj. The follow-
ing are semi-empirical equations for an explosive CaHbOcN:
Q
_ 28.9 b + 470 (c - b12) + Mtj (9)
max - MW

32. 6 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
TABLE 3. Calculation of pressure developed by detonation
%
Explosive Pexp Pcalc deviation
kbu (Pcalc-Pexp)
TNT 1.62 212 197.8 -6.7
1.30 123 127.4 +3.6
1.14 94 97.9 +4.1
RDX 1.80 347 342.5 -1.3
1.63 283.7 280.8 -1.0
1.40 213 207.1 -2.8
1.20 152 152.2 +0.1
HMX 1.90 393 380.9 -3.1
PETN 1.77 350 332.1 -5.1
1.67 300 295.7 -1.4
Tetryl 1.70 263 252.8 -3.9
where:
Qmax is the maximum possible heat of detonation in kcal/kg,
MW is the molecular weight of the compound.
The heat of detonation at the density P gfcm3
is Qp, and equation (10)
makes it possible to calculate:
Qp =Qmax [1 - (0.528 - 0.1 65pX1.4 -0)]
where: 0 is 'oxygen coefficient' calculated from equation (11):
c
0=----
'lJl + 2b/2
When
(10)
(11)
o~ 1.4, Qp =Qmax'
Another more complicated formula was worked out for explosives with a
high content of hydrogen and low value of0, for example 0 < 0.4.
The calculated figure for some common explosives are given in Table 4.
The average deviation is 2.3% and at p > 1.0 it is 1.8%.
In another paper Pepekin, Kuznetsov and Lebedev [33] worked out more
complicated equations which made it possible to calculate the rate of detonation
ofexplosives with a bulk formula Ca Hb Dc Nd Fe at a given density PI gfcm3
•
The following are equations given by these authors:
a b
0.135 a -b + 2] b -b + 0.4 (c+d+e)
K a+ a+
BB MW
(12)

33. INTRODUcnON
TABLE 4. Calculated and experimental data for the
heat ofdetonation
7
Compound
TNT 1.00
1.60
Picric acid 0.90
1.70
Tetryl 0.98
1.69
Nitroguanidine 0.80
1.58
Cyclonite (RDX) 1.10
1.70
Octogene 1.30
1.80
PETN 0.90
1.70
and
Qcalc Qexp Qmax
kcal/kg
830 860 1288
1000 1030
880 830 1282
1030 1010
980 960 1431
1150 1160
970 980 1102
1030 1060
1160 1190 1481
1280 1290
1200 1210 1477
1300 1300
1260 1300 1526
1340 1350
. %
n =KBB PI
where:
KBB the coefficient of the composition of the compound,
n the number of molecules in the products of the detonation,
PI the density of the explosive.
The rate of detonation D m/s can be calculated from formula (14)
D'l =8.0 (Q +R)
where Qis the heat of detonation in kcal/kg calculated from formula (10),
(13)
(14)
where nz is the number of molecules in the products of detonation.
Pressure is calculated from equation (I6):
P =PI D2
(XI - l)/xl (16)
where X I is the experimental degree of compression in the front of the deton-
ation wave where density is p:
XI =LPI
The calculated and experimental data for D and P are collected in Table S.
Mean deviation is ca. 1.4%.

34. 8 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
TABLE 5. Calculated and experimental data for D and P
Compound PI Q KBB %1 Dealc Dexp Pealc Pexp
m/s kbar
TNT 1.64 1010 0.0202 1.38 6900 6940 215 220
Picric acid 1.80. 1173 0.0207 1.37 7600 7700 297
Tetryl 1.70 1150 0.0215 1.37 7480 7560 257 263
Nitroguanidine 1.70 820 0.0298 1.31 8140 8200 266
Cyclonite (RDX) 1.802 1300 0.0260 1.34 8740 8800 349 347
Octogene (HMX) 1.903 1320 0.0260 1.33 9100 9150 390 393
PETN 1.77 1375 0.0243 1.36 8500 8370 338 350
TACOT 1.85 1044 0.0201 1.37 7310 7250 267 263
Recently Bernard [34] worked out a different fonnula for the rate of de-
tonation based on his kinetic theory of detonation [35]. His equation for the
correlation of the rate of detonation and the density PI in the shock wave front
is as follows:
_ PI k To dDmax --- -- .
Pmax h
(17)
Dmax is the experimental rate of detonation at an infmite diameter and maxi-
mum density Pmax,
k the Boltzman constant,
h the Planck constant,
To the initial temperature of the explosive,
d the mean molecular diameter.
Bernard applied his equation to a number of nitrate esters at room tempera-
ture.
Some of his results are shown in Table 6.
TABLE 6. Density in front of the shock wave and
experimental rate of detonation
Substance Dmax Pmax PI
m/s
Nitroglycerine 7700 1.6 2.57
Ethylene glycol dinitrate 8000 1.49 2.78
PETN 8600 1.77 2.94
Hexanitrate of dipentaerythrit 7450 1.63 1.93
Mannitol hexanitrate 8260 1.73 2.43
Methyl nitrate 8000 1.20 2.61
A plot of log Dmax against log PI gives a straight line.
Bernard and co-workers [51] extended his calculations to the rate of deton-
ation of C·nitro, O-nitro and N-nitro compounds by using two equations:

35. and
where:
INTRODUcnON
Demax = J!.L ~ To ( 6M_) ~
00 Pmax h .iT N Pmax
D'J =CoW/n)
9
(17a)
(l7b)
h is the Planck constant,
M denotes the mean molecular mass of the products,
N Avogadro number,
Co concentration of molecules on the surface of the explosive,
n number of the nitro groups in the molecule,
a exponent varying from 1.5 to 2.
A characteristic feature of the calculation by Bernard is that he does not use
the enthalpy of detonatipn but considers that the density Pt in the shock front,
that is, the compression by the shock wave is decisive for the rate of detonation.
The groups 'explosofores', such as NO:z, N3 are particularly strongly com·
pre:'sed. Thus pdPmax for dinitrobenzene is 1.40 and for picric acid is 1.88. For
azides it is approaching 1.7.
Two more papers should be mentioned: that by Aizenshtadt [52] and one
recently given by Rothstein and Petersen [53]. The latter authors like Bernard
[34, 51] point out that a simple empirical linear relationship exists between the
detonation velocity at theoretical maximum density and a factor F which solely
depends upon chemical composition and structure.
Thus:
D' =Do +(PTM - Po) X 3.0,
where
D' is calculated rate of detonation,
Do experimental rate of detonation,
PTM theoretical maximum density,
Po experimental density.
Factor F can be calculated:
(18)
[
nCO) +n(N) - n(H) + ~ - nCB) - n(D) - neE) ]
F= lOOX 2n(O) 3 1.75 4 5 -G (19)
MW
where G =0.4 for liquid and G =0 for solid explosives. A =1if the compound
is aromatic, otherwise A =0 and MW =molecular weight.
en Vo1.4 - I

36. 10 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
The other expressions:
nCO) = number of oxygen atoms,
n(N) = number of nitrogen atoms,
n(H) = number of hydrogen atoms,
nCB) = number ofoxygen atoms in excess of those already available to fonn
CO2 and H2 0,
n(e) = number of oxygen atoms double bonded to carbon as in C=0,
neD) = number of oxygen atoms singly bonded directly to carbon in
C-0 - R linkage where R =H, Nl4 or C.
neE) = number of nitrate groups either as nitrate-esters or nitrate salts.
The relation between D' and F can be expressed by the linear equation
D
' = F-0.26
0.55 .
(20)
The deviations between the calculated and experimental values in 95% of
explosives is of the order of 5%. Some of the results are given in Table 7.
TABLE 7. Calculated and experimental data ofD.
Calculated values of the factor F
Substance TM D F Do Deviation
(calc) (exp) %
TNT 1.65 6960 3.93 6670 -4
TNB 1.64 7270 4.26 7270 0
Picric acid 1.76 7500 4.31 7360 -2
HNB 2.0 9500 5.27 9110 -4
Tetryl 1.73 7910 4.54 7180 -2
Nitroguanidine 1.72 8160 4.81 8270 +1
EDNA 1.71 8230 4.83 8310 +1
Cyclonite (RDX) 1.83 8850 5.18 8950 +1
Octogene (HMX) 1.90 9140 5.24 9050 -1
Nitroglycerine 1.60 7100 4.35 7440 -3
DGDN 1.38 6760 3.97 6750 0
PETN 1.71 8290 4.71 8090 -2
DIN" 1.67 8000 4.63 7950 -1
TACOT 1.85 7250 4.14 7050 -3
It appears that the calculation of important parameters of detonation is still
in progress and further improvements with two basic methods:
(l) taking into account the enthalpy ofdetonation,
(2) taking into consideration the kinetic theory of detonation.
The problems are tackled in a few monographs: the earlier ones: [54-60]
and more recent by Fickett and Davis [24] and Mader [61].
Yoshida and co-workers [88] applied molecular orbital theory (Dewar's
MINDO method) to calculate the heat of formation of explosives.

37. INTRODUCfION 11
A more detailed discussion of the problems of the theory of high explosives
ue outside the scope of the present book.
SENSITIVITY OF EXPLOSIVES TO IMPAcr
The experimental fmding ofW'cihler and Wenzelberg(Vol. I, p. 3)gives a general
estimation of the sensitivity of nitroaromatic explosives to impact as a function
of the character and number of substituents to the benzene ring. On the other
hand T. UrbaJiski [36] expressed the view in 1933 that the sensitivity of solid
explosives to impact is a complicated function of a few factors, among which the
most important are:
(a) sensitivity to high temperature,
(b) sensitivity to friction.
This was based on two· observed factors:
(l) similarity of the curves of the sensitivity of mixtures of explosives to
impact and sensitivity to temperature,
(2) the se.ape of the curves of sensitivity of solid mixtures to impact indi-
cates that the sensitivity of mixtures is greater than that of the compon-
ents due to the friction of particles of two different solid substances.
In tum, the friction can obviously generate a high temperature (Bowden
and Tabor [37]).
The related curves are given in Vol. III, pp. 250,251,262 and reproduced now
in Fig. 1. Both curves (T-sensitivity to elevated temperature, M-sensitivity to
impact) are clearly composed of two parts: I and II. (Curve Twas established by
determining the temperature of ignition of the samples of 5 g in test tubes
placed in wood alloy at 150°C by increasing the temperature of the alloy at the
rate of 10°C/min. The sensitivity to impact is expressed in ordinates as the
work in kg/cm2
produces 50% of explosion). The sensitivity to impact is mani-
fest by a shape where fraction I of the curve M indicates the increase of the
sensitivity of compound A by adding a less sensitive compound B. This is ration-
alized in terms of the friction between two foreign solid particles.
The sensitivity of mixtures to impact through friction is particularly notice-
able in examples of mixtures of TNT with hard crystals of ammonium nitrate
(Fig. 70, Vol. III, p. 262).
Papers have been published on the increase of sensitivity to impact by adding
gritty compound, Ubbelohde et ai. [38] and recently Scullion and McCormack
[39] .
Bowden and Yoffe [40] have developed the well known concept of 'hot
spots' and that the initiation of explosion stems from 'hot spots' created by ther-
mal factors and crystal hardness and shape. Small bubbles of air included in

38. 12 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
o
100%8
so
SO
lOO%A
o
(21)
FIG. 1. Sensitivity to impact (M) and initiation temperatures (7') of mixtures
of two explosive components: A and B. (According to T. Urbanski [36).
liqUid explosives (e.g. nitroglycerine) also increase the sensitivity to impact
through the adiabatic compression of air and a rapid increase in temperature. See
also Lovecy [41].
Kamlet [42, 43] also agrees with the thermal character of the sensitivity to
impact. He developed an ingenious method of calculating the sensitivity of ex-
plosives to impact. For similar explosives he found a linear relationship between
logarithmic 50% impact heights and values of oxygen balance OBI 00. The latter
value is calculated for C- H- N-0 explosives from the equation:
DB - l00(2no - nH - 2nc - 2ncoo)
100 - MW
where no, nHt nC represent the number of atoms of the respective elements
in the molecule and ncao is the number of carboxylic groups.
Fifty per cent impact heights on a logarithmic scale give a straight line.
A few figures are given (Table 8) for typical nitroaromatic compounds [42]
and nitramines [43].

39. INTRODUCTION
TABLE 8. Sensitivity of explosives to impact
13
Explosive
TNT
TNB
Picric acid
Styphnic acid
RDX (Cyclonite)
HMX
EDNA
OB100
-3.08
-1.46
-0.44
+0.41
o
o
-1.33
h 50%(cm)
160
100
87
43
24
26
34
Cherville and associates [44] have examined a number of explosives in a mass
spectrograph. Particularly important and reproducible were results at 77K. The
formation of N02 was readily established in the spectrograms. The authors
introduced a concept of the radiochemical yield GN02
of the formation of N02 •
A considerable difference exists between the values of GN02
of nitramines and
nitroaromatics. They correlated the values of GN02
with those of the sensitivity
of explosives to impact, friction and high temperature (temperature of initi-
ation ti at the rate of heating SOC/min): Table 9.
TABLE 9. Sensitivity of explosives to impact and friction
Difference
Sensitivity Sensitivity between ti and
Explosive to impact to friction temp. of GN02
kgm kg! melting point tm
ti-tm
PETN 0.31 4.5 79 3.8
RDX 0.45 U.5 56 0.9
Octogen (HMX) 0.52 10 50 0.8
Tetryl 1.1 27%at 36 kgf III 0.006
Picric 3 7%at 36 kgf 178 0.001
TNT 48%at 5 kgm 29.5 209 0.001
Nitroguanidine no explosion no explosion no inflammation 0
A very important contribution to the knowledge of the sensitivity of explos-
ives to impact has been given by Delpuech and Cherville [4S]. They came to the
conclusion that the basic criterion of sensitivity of explosives lies in the distri-
bution of electrons in their ground state and the comparison with that in the
excited state. With the advent of quantum mechanical methods, and particu-
larly that of tN.D.O. [46] they were able to calculate the distribution of elec-
trons in explosives, thus introducing a new and original criterion of sensitivity
of explosives. For quantitative estimation they mtroduced a parameter b.Co/1,

40. 14 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
where
liC' is the dissymmetry of the distribution of electrons in the ground state,
I the length of the bond C- N02 , N- N02 or 0 - N02 •
The following are a few figures thus calculated (Table 10). Higher sensitivity
of explosives is manifested by a higher liC'll. The data for excited state liC
x
II
were C?alculated with the method C.N.D.o-S/C.l. [47].
TABLE 10. Sensitivity of explosives to impact
Explosive Bond· CO CO CX
-,- -,-
DNB C(I)-N02 0.539 0.363 0.308
TNB C(5)-N02 0.575 0.391 0.303
RDX N(I)-N02 1.044 0.764 0.343
HMX (6) N(I)-N02 0.937 0.673 0.345
EDNA N-N02 0.880 0.676 0.499
Tetryl N-N02 0.841 0.624 0.478
PETN O-N02 0.878 0.645 0.417
• The numben in brackets indicate the position of atoms of C and N in the molecule
as given in their formulae based on crystaUographic analysis (Vol. I, 181; 11,372,385).
The relative change 6 from liCo to liCx can be expressed by equation (22)
li = 100 (liC
X
-liCO) (22)
liCo
Delpuech and Cherville [45b] suggest using values of liCxII and 6 as data
indicating the tendency of explosives to decompose under impact. This would
be particularly advisable with new explosives which although their structure is
known, possess unknown properties.
While examining the shape of the curve of the sensitivity to impact of TNT at
different temperatures (Vol. I, p. 320, Fig. 74). T. UrbaDski [48] advanced an
hypothesis that the increase of sensitivity is due to the increase of entropy (S)
~d therefore decrease of free energy G =H-TS. A critical change is at the melt-
ing point of TNT - ca. 80°C which is well known, is manifested by a rapid in·
crease of entropy (Fig. 2). Cruchaud [79] drew attention to the electric pheno-
mena which accompany the shock and friction produced by the impact. Charg-
ing with static electricity is an important factor influencing the explosion
according to this author.
Attention is drawn to two monographs dealing with the initiation of explos-
ives by impact: solid explosives by Afanasyev and Bobolev [49] and liquid by
Dubovik and Bobolev [50]. The authors based their views on the considerable

41. INTRODUCI10N
G=H-TS
--_ G
-----~
I ,
,,'
'
'
'
15
m.p. temp.
FIG. 2. Sensitivity to impact of TNT (M) and Gibbs free energy (G) as a
function of temperature. Melting point: m.p. (According to T. Urbanski [481).
work carried out by Khariton, Andreev, Belyaev, Kholevo, Sukhikh, Avanesov,
Bolkhovitinov, Bawn and their own experiments. The authors agree with the
thennal nature of the sensitivity of explosives to impact. However most of the
problems raised by the authors of the monographs are outside the scope of the
present book.
Senntivity of high explosives (HE) to initiation by an initiating explosive
('gap sensitivity', 'initiability') is less defmed than the sensitivity to impact and
cannot be expressed in absolute units. The sensitivity of HE to initiation is
usually detennined:
(1) by the amount of the initiating explosive in the detonator (this method is
also used to detennine the 'initiating strength' of primary explosives),
(2) by transmitting the detonation from one charge to another through air
or other medium (water or a sheet of metal or a polymer) of different
thickness,
(3) by detennining the critical diameter, that is the minimum diameter
which is able to transmit the detonation.
It is weD known that the HE can be arranged in the sense of decreasing sensi-
tivity to detonation: O-nitro, N-nitro and C-nitro compounds.

42. 16 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
Cachia and Whitbread [63] described a 'gap' test of different explosives and
detennined the minimum gap thickness that inhibits detonation.
Recently Ahrens [64] reviewed the problem of detennination of the sensi-
tiveness of explosives to initiation.
Sensitivity to friction is also less dermed than the sensitivity to impact and
can be expressed only by figures comparative to a standard. By decreasing
sensitivity the explosives can be arranged as follows [65] :
initiating explosives (with exclusion of azides),
O-nitro compounds,
N-nitro compounds and metal azides,
C-nitro compounds.
The sensitivity of explosives to heating, naked flame, impact and friction is
decisive in the international rules for railway traffic 'RID' (Regiement Inter-
national Concernant Ie Transport des Marchandises Dangereuses) [65]. Ana-
logous rules'ADR' are concerned with international motor traffic [66].
Important reviews have appeared on the sensitivity and initiation of ex-
plosives [67,68] .
Action ofUltrasonic Waves and Laser Pulse
Early work on the action of ultrasonic waves on explosives indicated that
such sensitive substances as nitrogen iodide could explode [73, 74] but that
silver fulminate could not be brought to detonation [74].
Some experiments by Wolfke [69] have shown that high intensity waves
were required to bring mercury fulminate to detonation. Negative results were
obtained by Renaud [75] who pointed out that the positive results of Marinesco
[74] were due to the mechanical action of pushing crystals by the oscillator.
This query was recently solved by Leiber [76] who stated that the detonation
of nitroglycerine by ultrasonic waves can occur provided that the explosive con-
tains bubbles and the nature of the effect is mainly thennal bringing the tem-
perature to 300-50(tC through the adiabatic pressure of the order of 33 bar.
Mizushima and Nishiyama [77] examined the action of laser and found that
compressed explosives can be brought to decomposition by a giant laser pulse.
Loose explosives cannot detonate. They examined initiating explosives, PETN,
RDX, TNT and Tetryl.
Action ofIrradiation
Numerous publications particularly in recent years have been dedicated to the
sensitivity of explosives to various fonns of irradiation.
Bowden and Yoffe [70] reviewed the literature and their own work on the
decomposition of initiating explosives by irradiation with electrons, neutrons,

43. INTRODUcnON 17
3.80
0.90
0.80
0.006
0.001
0.001
o
filaion products, a-particles, X-rays and 'Y-rays.
Recently two abundant reviews appeared in the Encyclopedill of Exploma
edited by Kaye and Hennan [71,72].
Thus Avrami [71] reviewed radiation effects on explosives, propellants and
pyrotechnics. Here are some of the main conclusions taken from the work of
Avrami and numerous authors: initiating explosives are decomposed under
irradiation with a-particles, neutrons, 'Y-radiation, electron irradiation and
underground testing. Among the reviewed papers Avrami reported his own
work on the influence of C060
gamma radiation on the detonation velocity
of explosives: they all show a fall in velocity after irradiation. Cyclonite (EDX)
appem to be particularly sensitive, less sensitive are PETN and HMX. Aro-
matic compounds such as TNT and Tetryl seem to be still less sensitive.
A good stability is shown by heat resistant explosives: TACOT, DATB
(Diaminotrinitro-) and TATB (Triaminotrinitrobenzene) (Chapter VII).
Helf [72] described the technique of radiation gauging in energetic materials.
A remarkable paper has been published by Cherville and co-workers [80].
They examined the behaviour of a few secondary explosives to the irradiation
from C060
and introduced the value GN02 : the quantity of N02 by irradiation.
They found the values of GN01
being correlated to the ability of explosives to
detonate. The following are the figures for ~02 :
PETN
Hexogene, Cyclonite (RDX)
Octogene (HMX)
Tetryl
Picric acid
TNT
Nitroguanidine
Influence ofHigh Temperature
The behaviour (including the decomposition) of explosives at high tempera-
ture is one of their important characteristics. With the advent of DSC (differen-
tial scanning calorimeter) high precision can be reached of the examination of
endo- and exothennic changes in substances with the increase of temperature.
This was reviewed by Collins and Haws [81]. The pioneering work on DSC by
Tucholski in 1932-33 [82] should be recalled (see also Vol. I, p. 525).
Two Soviet monographs appeared [83, 84] both dedicated to thennal de-
composition and bUming of explosives, and a review by Maycock [85].
INCREASING 11fE STRENG11f OF EXPLOSIVES BY ADDING METALS
A popular method of increasing the strength of explosives is by adding alu-
minium and less frequently calcium silicide, ferro-silicon, silicon (Vol. III,
p.266).

44. 18 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
1200 kcal/kg
1380
1420
1520
1690
1890
cal. val.
The following figures illustrate the action of aluminium on the calorific value
of RDX (Cyclonite) given by Belaev [86J:
RDX+ AI 0% AI
5%
10
15
20
33
Recently the addition of Boron or its compound with hydrogen, for example,
'ortho-borane' (C2 H12 BIO ) was investigated by Pepeldn, Makhov and Apin
[87J. They examined mixtures or" PETN and Cyclonite with boron or ortho.
borane. The calorific value of Cyclonite-Boron reached a maximum (1890
kcal/kg) with ca. 16% B. PETN with ca. 22% reached a value ofca. 2050 keal/kg.
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46. 20 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
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59. K. K. ANDREEV and A. F. BELYAEV, ObozongU, Moscow (1960).
60. Ya. B. ZELDOVICH and Yu. P. RAIZER, Plryrtcl of Shock WlJPeI and High Tempera·
tII~ Hydrodynamic Phenomena. Nauka. Moscow (1966).
61. 01. MADER, Numerical Modeling of Detonation" University of California Press.
Berkeley (1979).
62. D. SMOLE~SKI, Detonacja Materialow Wybuchowych, MON, Wuazawa (1981).
63. G. P. CACHIA and E. G. WHITBREAD, Proc. R. Soc. A. 246, 268 (1958).
64. H. AHRENS, PropellJzn" and Explo,;,e, 3, 49 (1978).
65. R. MEYER, Explo,imoffe, p. 227, Verlag O1emie, Wcinheim (1979).
66. R. MEYER. Explosi,e" p. 230, Verlag Chemie, Weinheim (1977).
67. Proc. R. Soc. A, Collective volume (Eels F. P. Bowden and W. E. Garner) 246 (1958).
68. Sensitivity and Hazards of Explosives. Ministry of Aviation, E.R.D.E., London, 1963
and references therein.
69. M. WOLFKE, unpublished work done at Technical University. Warsaw. 1939.
70. F. P. BOWDEN and A. D. YOFFE, Fa,t Reaction, in Solid" Butterworth, London
(1958).
71. 1.. AVRAMI, in, J::ncyclopedill of Explosi,e, and RelJzted Item" Vol. 9, pp. R5-R67.
(Eds S. M. Kaye and H. 1.. Herman) ARRADCOM, Dover, New Jersey, 1980.
72. S. HELF, in, l:;'ncyclopedill (as above), Vol. 9, p. R76. (Eds S. M. Kaye and H. L. Her·
man) ARRADCOM, Dover, New Jersey, 1980.
73. W. T. RICHARDS and A. 1.. LOOMIS, J. Am. Chem. Soc. 49, 3086 (1927).
74. M. N. MARINESCO, Compt. rend. 201. 1187 (1935).
75. P. RENAUD, J. Chim. Phy.. 48.336 (1951).
76. C. O. LEIBER, J. Ind. Expl. Soc., Japan 35, 63 (1974).
77. Y. MIZUSHIMA and I. NISHIYAMA, J. Ind. ExpL Soc., Jllpan 35,76 (1974).
78. H. J. EMELEUS, Endea,our 32, 76 (1973) and references therein.
79. M. CRUCHAUD, &plo,i"t. 18,16 (1970).
80. J. CHERVILLE, B. LINARES, S. POULARD and C. SCHULZ, 11rlrd Sympo,ium on the
Stability ofExplo,i,e" p. 47, (Ed. J. Hansson), Ystad, 1973.
81. 1.. W. COLLINS and 1.. D. HAWS, Thermochim. Acta 21,1 (1977).
82. T. TUCHOLSKI, Acta Phy.. Polon. I, 35 I (1932); Roczniki Chern. 13,435 (1933).
83. K. K. ANDREEV, Thermal Decompo,ition and Burning of Explosi,e, (in Russian),
Izd. 'Nauka', Moscow, 1966.
84. A. P. GLAZKOVA, Cotaly,i, of Burning Explo,i,e, (in Russian), Izd. 'Naub', Moscow,
1976.
8S. J. N. MAYCOCK, Termochim. Acta I, 389 (1970).
86. A. F. BELAEV, Burning, Detonation and Work of Explolion of Conden,ed Sy,tem"
p. 226, Izd. 'Naub' Moscow (1968).
87. V. I. PEPEKIN, M. N. MAKHOV and A. Ya. APIN, Fizilca Goreniya ; Vzry,a, 135
(1972).
88. M. ARAI, T. ANDOH. M. TAMURAandT. YOSHIDA. I. Ind. £xpl. Soc.lapan4I.H(l9HO)-
from the translation of the Bureau of Mines U.S.A.

47. CHAPTER 1
NITRATION AND NITRATING
AGENTS
(Vol. I, p. 4)
A considerable number of papers were dedicated to the problem of nitration in
the years following the publication of Vol. I.
Among nitrating agents the most important still remain nitric acid-sulphuric
acid mixtures, but some other very efficient nitrating agents related to nitric
acid have been found and are in use, mainly on a laboratory scale.
NITRIC ACID (Vol. I, p. 6)
Considerable attention is currently being paid to nitric acid (and nitrogen
dioxide) because of their wide use, not only for nitration, but also as oxidizing
agents in rocket propellant systems. A review has recently been published by
Addison [1] .
Pure nitric acid free of nitrogen dioxide, so called white fuming nitric acid
(WFNA), is in use as an o'jdizer and for nitration of some compounds (e.g.
hexamethylene tetramine plexamine], Vol. III, p. 87).
However WFNA is relatively unstable and with time develops a certain
amount of dinitrogen tetroxide. More stable for rocket propulsion is red fuming
nitric acid (RFNA) which contains ca. 14 wt% N20 4 • It is formed from WFNA or
from nitric acid with added N10 4 • RFNA is the equilibrium product formed
from both extremes of the concentration range:
HN01 -HNO] + N1 04 + H1 0-HNO] + N1 04
WFNA 84.S% 14% 1.5% (in excess, (1)
subject to
RFNA evaporation).
RFNA is more reactive than WFNA, N20 4 being a suigeneris catalyst of the
oxidation reactions. Subsequently RFNA is more recommended in rocket fuel
than WFNA, but should be avoided in most nitration reactions. Dinitrogen tetr-
oxide (usually given in analytical data as N02 ) is present in spent acids contain-
21

48. 22 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
ing nitric and sulphuric acids and is formed in the course of nitration as a result
of the oxidation of the nitrated substances. The content of NO:z in the spent
acid can be as high as 5%. Commercial 'fuming nitric acid' ('anhydrous nitric
acid') usually contains less than 1% NO:z and is used for the nitration of hex-
amine.
Pure nitric acid (WFNA) can be obtained by distillation of nitric acid from a
mixture of concentrated nitric acid (d 1.50 at 25°C) and concentrated sulphUric
acid, under reduced pressure at room temperature. A white crystalline solid
results with the following properties [l]:
m.p. - 41.6°C
b.p. + 82.6°C
d - 1.549 at O°C
viscosity 10.92 cP at O°C
dielectric constant 50 ± 10 at 14°C
surface tension 43.5 dY/em at O°C
specific conductivity 3.77 X IO-:z ohnfl em-l .
The latter two figures are high due to hydrogen bonding (Vol. I, p. 7, Fig. 1).
The data in Fig. la (VoL I, p. 7) should be slightly altered on the basisofmore
recent measurements by micro-wave spectroscopy [2,3]. They are now given in
Fig. 3.
o o
FIG. 3. Structure of the molecule of nitric acid (2, 3J •
It is well known that nitric acid forms an azeotropic solution with water. It
contains 68.5 wt% HN03 and boils at 122°C under standard atmospheric press-
ure.
Cryoscopic meuumnentl (Vol. I, pp. 15-16) have shown that only a little
Oftr 3% of pure nitric acid is dissociated at --.400C according to the equation:

49. NITRATION AND NITRATING AGENTS
2HNO] ;;;::= NO;- + NO;- + H20
1.2 1.7 O.S wt~.
23
(2)
Water is in the form of the nitric acid hydIate.
A few more spectroscopic data for nitric acid should be added to those pre-
viously given (Vol. I, p. 22). Vitse [31d.] has found bmds in nitric acid: 1680,
1300 and 930 em-I assigned to N02 and band 3200 em-I to OH stretching
vibrations.
It is now generally accepted that the nitronium ion NOt is the main nitrat-
ing agent. Although most industrial nitrations are carried out by nitric acid-
sulphuric acid mixtures, some compounds can be nitrated with nitric acid alone
(production of tetryl, Vol. III, p. 42). Some products; such as PETN (Vol. II,
p. 185) are usually obtained by nitration with nitric acid alone md Cyclonite
(if made by nitration) is produced exclusively with nitric acid free of N2 0 ..
(Vol. III, p. 87).
Although the nitronium ion is the nitrating agent, there are known examples
when nitration can occur in media in which the concentration of NOt is too
small to be detectedspectroscopically(Vol.I,pp. 25,48). This waspomted out by
Bunton and Halevi [4] who succeeded in nitrating aromatic compounds with
40-60% aqueous nitric acid. Bunton and co-workers [5, 6] showed that the
nitronium ion was an intermediate in both oxygen-exchange and aromatic
nitration in the sense of reactions:
2HNO] = H1 NOt + NO;.
H1 NOt;::: NOt + H10.
(3)
(4)
Hydrated nitronium ion (nitracidium ion) H2 NOt is a source of the nitrating
+apnt N02 •
It was reported [7] that nitration of l,S-dinitro-naphthalene can occur with
70% nitric acid to yield trinitro-naphthalenes.
The problem of nitration with aqueous nitric acid was reviewed by Hanson
a,nd associates [8]. They confirmed the idea ofnitracidium ion being a nitrating
agent and pointed out that attention should be paid to the presence of nitrous
acid in the system, as nitration with dilate nitric acid can proceed through the
nitrosation by nitrous acid formed as the result of oxidation-reduction. T.
Urbanw and Kutkiewicz [9] (Vol. I, p. 85) found that8-hydroxyquinoline can be
nitrated by boiling with 0.5% nitric acid to yield S,7-dinitro-8-hydroxyquino-
line. It was also found that 8-hydroxy-S-nitroquinoline yielded the same dinitro
derivative.
As far as the mononitration of phenol and the formation of 8-hydroxy-S-
nitroquinolJne can be explained in terms of the conventional mechanism of

50. 24 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
nitrosation followed by the oxidation of nitroso to the nitro group (p. 23), this
mechanism could not explain the formation 5,7-dinitro-S-hydroxyquinoline
from mononitro compound. The mononitrophenols cannot be nitrosated with
nitrous acid and SUbsequently the formation of the second nitro group cannot
occur through nitrosation. Nevertheless, the reaction of formation of the dinitro
compound from the mononitro product is preceded by the oxidation and evo-
lution of N02 • This would apparently sugest that nitrosation (as shown above)
is not possible with 8-hydroxy-5-nitroquinoline.
Also Ross and co-workers [87] pointed out that the accepted scheme of
nitration of phenol in 56.2% sulphuric acid through nitrosation prior to nitra-
tion, is inconsistent with the results and expressed the view that another route
should exist.
The author of the present book suggests the solution of the problem of
nitration of phenols with dilute nitric acid in a two-fold way:
(I) Through oxidation (which always accompanies nitration and particularly
the nitration of phenols) N02 is evolved and the well known reaction
occurs:
(5a)
(2) The dilute nitric acid originally present in the solution and also formed
in reaction (Sa) can given rise to NOt in a readily oxidizable medium
according to scheme (5b) rationalized by the author [I 12] :
(5b)
Reaction (5b) can take place in readily oxidizable mediums such as phenols
and aromatic amines.
Usanovich [128] has drawn attention to the amphoterism of HN03 which. to
follow ideas of Hantzsch (Vol. 1, p. 12) HN03 is a base when interacting with
H2S04, Usanovich and his associates found that HN03 is a base towards
CChCOOH but an acid towards CH3CO OH. With the amphoteric behaviour
of HN03 the dilution of nitric acid with such substances as (H2S04• H3P04)
toward which HN03 is a base or which (H20. CH3COOH) act as bases toward
HN03 promotes or hinders the nitration of aromatic compounds respectively.
NITRIC AND SULPHURIC ACID
Mixtures of nitric and sulphuric acids contain nitronium sulphates which have
been described by Ingold and associates, Woolfand Emeleus (V01.1, p. 19). Reval-
lier and co-workers [10] have found by Raman spectroscopy and vapour press-
ure measurements, that com~unds made by acting with S03 on nitric acid are
salts of nitronium ion (N02 ) and sulphate anions. Vitse [11,] establilhed the
structure of the compound N2 Os .4S03 as nitronium ion salt by X-ray crystal-
lography. The salta of pyrosulphuric acid (Vol. I, p. 12) can be present only in a

51. NITRATION AND NITRATING AGENTS 25
mixture of nitric acid with oleum or 503 . lhey are described in the paragraph
on nitronium salts (p. 27). The presence of NOt in various solutions was dis-
cussed in Vol. I, pp. 14-49.
The basicity of nitric acid in the sense of the dissociation N02 0H iii!' NOt +
Off"" in concentrated sulphuric acid was recently studied by Marziano et al.
[12]: the ionization ratio NotlHN03 of nitric and 80-96% sulphuric acids has
been evaluated by Raman and ultraviolet spectroscopy. The function pK. of
nitric acid as a base was calculated pKa = -15.2.
As far as the activity of the nitrating mixture (Vol. I, p. 29) is concerned, a
novel approach to the problem was recently developed by Marziano and associ·
ates [13]. In a series of papers on thermodynamic analysis of nitric acid with
sulphuric or perchloric acid these authors introduced a new function of the
activity coefficient Me:
Me =log fB fH+
FBH+
where fB is the activity coefficient of the nitrated substance, fH+ activity co-
efficient of the proton H+.
Effects ofAdding Salts on Nitration in Sulphuric Acid
A few authors have examined the effect of adding salts on the rate of nitra-
tion in sulphuric acid.
Thus Surfleet and Wyatt [14] studied the nitration of benzenesulphonic acid
in sulphuric acid and found that the addition of hydrogen sulphates of various
metals increases the nitration rate. The most marked effect occurred with cal·
cium and barium hydrogen sulphates. An explanation of the effect was sought
in terms of the Bransted salt-effect theory. It was suggested that the main in-
fluence of ionic solutes is in the activity coefficient of the nitrated substance
(fB) since the activity coefficients of the other two species, the nitronium ion
(fNOt) and the similarly charged transition complex <tt)as a ratio in the Bron·
sted equation and would be approximately equally affected by changes in the
ionic environment. The view was expressed that reactions involving only ionic
species would exhibit small salt effects.
Bonner and Brown [15] expressed the view that the increase in reaction rate
due to added salts is similar to the increase initially resulting from the addition
of water to anhydrous sulphuric acid, attaining the maximum at ca. 90% acid.
They supported it by examining the rates of nitration of trimethylphenyl-
ammonium ion and l-chloro-4-nitrobenzene. When ammonium sulphate was
added, the rate increased more than X20 their value in the anhydrous acid. On
the nitntion of cenulose with nitric acid in the presence of inorganic salts (see
Vol. II, p. 346).

52. 26 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
Nitric Acid and Trifluoromethane Sulphonic Acid
A very interesting nitrating mixture has been reported by Coon, Blucher and
Hill [J6J. It was composed of nitric acid and trifluoromethane sulphonic acid:
CF) .S03 H. It contains nitronium salt: NOt CF3SO;-. The major difference
between the aromatic nitration with this and other nitronium salt is an ex-
tremely high reaction rate.
The nitration of toluene with such a mixture is described in the chapter
dedicated to the nitration of aromatic hydrocarbons.
Nitric Acid and Hydrofluoric Acid
NMR spectroscopy revealed [17J that NOt is also formed by acting with HF
on nitric acid, viz.:
(6)
Earlier the presence of Not in nitric acid-hydrofluoric acid solution was
postulated by Vorozhtsov Jr and his School [18J. Vorozhtsov Jr and associates
[19] found that nitric acid-hydrofluoric acid solution can produce both: the
nitration and fluorization of aromatic compounds through an ipso-attack (see
p. 50) of both NOt and F-.
Nitric and Phosphoric Acid
It is admitted that anhydrous solution of nitric and phosphoric acids contains
nitronium ion.
So far nitric-phosphoric acid mixtures have been mainly of theoretical inter-
est (Vol. II, p. 341). However recently a few attempts have been reported on the
nitration of toluene with nitric-phosphoric acid mixtures in order to reduce the
proportion of o-nitrotoluene and subsequently to increase the yield of para
isomer (Harris [.20]).
Nitric Acid and Acetic Anhydride
Nitric acid and acetic anhydride mixture is often used as a nitrating agent on
a laboratory scale. It is possible that nitronium ion is present in such solutions
[21 J. According to A. Fischer and associates [22, 23J nitric acid-acetic anhy-
dride mixtures contain nitronium acetate. Nitric acid-acetic anhydride yield not
only nitro compounds but can also produce an acetylation through the oxid-
ation and subsequent acetylation of the side chain [23J. Thus o-xylene sub-
jected to the action of nitric acid-acetic anhydride at O°C gave 16% 3-nitro-
and 33% 4-nitroxylene and 51% 3,4-dimethylphenyl acetate. The authors sug-
gested it as being the result of the prt!sence of oxonium ion CH) COO+N02 •
Nucleophilic attack on a ring carbon leads to acetoxylation.

53. NITRATION AND NITRATING AGENTS 27
Very often nitration with nitric acid-acetic anhydride solution is referred to
as nitration with acetyl nitrate (Vol. I, p. 44). Petrov and co-workers [24] experi-
mented with nitric acid and acetic anhydride with a small quantity of sulphuric
add at 3SoC on ethoxyvinylphosphates. The ester was.hydrolysed to yield a
nitromethane derivative:
CH)COONOl -OC1H~ (N)
(ROh P(O)CH =f1iOC1H~ • (RO)11'(0~Il-nl_OCOCH.l -:-:Nu"';'c':"'"le-oP~h~iie
N01 (7)
° H+- (ROh P(O) fH =N:::o=-- (RO)l P(OH)(,H2 N02 "
literature on the practical use of nitric acid-acetic anhydride includes also
some warnings on explosion hazards associated with the use of mixtures of fum·
ing (97%) nitric acid with acetic anhydride. Thus Brown and Watt [2S] demon-
strated that mixtures of nitric acid with acetic anhydride containing more than
SO% by weight of nitric acid can undergo a spontaneous explosion.
Dingle and Pryde [26] extended this warning also to mixtures containing
less than 50% nitric "acid. Particularly dangerous is the addition of a small quan·
tity of water or some mineral acids to such a mixture. Amixture containing 6%
nitric acid in acetic anhydride with 1.7% concentrated hydrochloric acid was
found to self·heat at 20°C and to fume-off vigorously at 60°C with gas eva·
lution.
Nitric Acid with Cerium Ammonium Nitrate or Tallium Nitrate
Considerable interest has been shown recently in the use of cerium (IV)
salts as oxidizing agents. Cerium (IV) ammonium nitrate can also be a nitrating
agent [125]. It can also act in the presence of acetic acid [119]. In the presence
ofnitric acid [120] it can form nitrate esters from the methyl group, viz.:
(see Chapter X).
Tallium (Ill) nitrate can also be used as a nitrating agent [119].
NITRONIUM CAnON (Not) AND ITS SALTS
Crystalline nitronium salts were first obtained as early as 1871 by Weber [27]
(see also Vol. I, p. 12). He gave the composition NzO,AS03.3HzO and
NzO, AS03 • HzO. Several similar salts have been obtained by a number of
authors [10, 28-30]. The most important contribution to the knowledge of
stoichiometry of NZO,.S03 and NZO,.S03.HZO complex-salts has been made
by Vitse [31].
AU these salts possess ionic structure comprising cation NOt bonded in
various proportions to HSO., HSzO:;-, SzO,z- etc.

54. 28 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
Some of the salts possess a great stability if protected from moisture. Thus
Werner compound N20,.4S03 .H20 has the structure' NOt H~O'" and m.p.
I05.6°C [lOa]. The compound 8N20,.20S03 •7H20 with the structure
(NOt)16S20,2-(HS20:;)4(HSO;)1O has m.p. 119.8°C. Its crystal structure
was determined by X-ray analysis [Ill as already mentioned (p. 28).
Other salts of nitronium ion and sulphuric acid have been previously des-
cribed (Vol. I, p. 19). Ingold and co-workers (Vol. I, p. 19) obtained crystalline
nitronium perchlorate which was relatively stable, but decomposed on storage
and was not further investigated.
R. J. Thomas, Anzilotti and Hennion [32] reported that boron trifluoride
could play the same part as sulphuric acid in the nitration of aromatics. Olah and
co-workers [33, 40] prepared and successfully applied a number of stable salts
ofnitronium ion in a relatively simple way:
NOt X where X = BF4, AsF.,PF.
and
(NOt)2 Y when Y = SiF.2-.
Particularly important is nitronium tetrafluoroborate obtained by adding
anhydrous HF to nitric acid in a solvent such as nitromethane or methylene
chloride and then saturating the solution with boron trifluoride (8):
(8)
An almost quantitative yield ofstable nitronium salts NOtBF;' can be obtained
in that way [34] and it is now commercially available [35]. It is a colourless,
crystalline very stable compound which decomposes above 170°C into N02F
and BF3 without subliming. It is a very strong nitrating agent [36].
Among other compounds nitric acid-boron trifluoride HN03 .2BF3 complex
(m.p. 53°C) obtained by Revallier and associates [37] proved by Raman spec-
troscopy to possess the structure of nitronium salt NOt (BF3 hOH- [38] .
Nitronium ion is able to form nitroxonium and pyridinium ions with ethers
and pyridine or coUidine respectively by acting on ethers and pyridine or colli-
dine respectively with nitronium tetrafluoroborate [39, 4Od] :
NOi Y-+ R-X-R --_.~
(9)
Y= PF'. BF-.
X = 0, S;R = Alkyl. H

55. NITRATION AND NITRATING AGENTS 29
• (10)
The nitroxoniurn and nitropyridiniurn (or nitrocollidiniurn) ions are efficient
nitrating agents. They also can fonn O-nitro compounds.
Nitronium hexafluorophosphate (Not PF;) is also a strong nitrating agent
according to Olah and Un [40b]. It can nitrate alkanes at 25°C to a small
yield of nitro compounds (2-5% for ethane to butane). Nitronium tetrafluoro-
borate in fluorosulphuric acid (FS03 H) possesses strong nitrating properties. It
can nitrate m-dinitrobenzene to sym-trinitrobenzene with a yield of 66% [40c] .
Among the salts of nitroniurn ions a very active nitrating agent is nitronium
trifluoromethyl sulphate (NOt CF3 SO;) as already mentioned [16].
Nagakura and Tanaka [41] explained a great reactivity of NOt by calculat-
ing its lowest vacant orbital and the highest occupied orbital of benzene. The
figures are -11.0 and --9.24 eV respectively. Other electrophilic reagents, such
as Br+ and Cl+ are less reactive. They gave values of -11.8 and -13.0 eV res-
pectively.
Nitronium salts are usually applied in an aprotic solvent [35]. Such is tetra-
methylene sulphone ('Sulfolan') used by Olah [40]. However, Giaccio and
Marcus [42] suggested acetic acid as a solvent. This, however, reacts with
nitronium tetrafluoroborate on standing at room temperature to yield acetyl
nitrate:
The nitrating action of acetyl nitrate differs from that of nitronium tetra-
fluoroborate [40]. Also the stability of acetyl nitrate is not satisfactory.
Dinitrogen Pentoxide (N"Os) (Vol. I, p. 105)
Dinitrogen pentoxide (nitric anhydride) can be a source of the nitronium ion.
As 'previously mentioned Titov suggested (Vol. I, p. 106) that dinitrogen pent-
oxide undergoes a heterolytic dissociation:
(12)
The infra-red bands of the ionic fonn at liquid nitrogen temperature have
been examined by Teranishi and Decius [43] and substantiated by Hisatsune
and co-workers [44] who also examined Raman spectra. They found A tempera-
ture dependence of the structure of solid N"Os which changed the covalent
structure O"N-O-N01. into ionic at temperatures from -175° to -80°C.

56. 30 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
The covalent structure is characterized by a bent of the central N-0 - N group.
Dinitrogen pentoxide readily forms nitronium salts. As mentioned, Weber
[27] and other authors [28-31] obtained a number of sulphates of NOt.
Bachman and Dever [45] prepared a complex with BF, which most likely
possesses the structure NOt BF,ONO;-. Kuhn and Olah [33] obtained nitro-
nium tetrafluoroborate by adding anhydrous HF as a solvent to N20 S and BF, :
(13)
T. Urbanski used N20 S in vapour phase or in a solution in nitric acid to
nitrate cellulose (Vol. II, p. 348) and starch (Vol. II, p. 430).
N2 Os was successfully used by Schollkopf and associates [46] to nitrate ali-
phatic diazocompounds to obtain eventually nitrodiazomethane [46b] and
dinitrodiazomethane [46c]. As the first step esters of diazoacetic acid were
nitrated with half a mole of N20 S in carbon tetrachloride at -20 to 30°C:
(14)
CF3 COOH
Nz C-COOR • N2 = CH + CO2 + ROH
I I
N~ N~
I II
Nitrodiazoester (I) is relatively acid-stable, but the COOR group can be
cleaved off by acting with trifluoroacetic acid in ether to obtain nitrodiazo-
methane (II) 02N-CH Nt m.p. 55°C. It is a substance which is sensitive to
impact and explodes on heating.
Nitrodiazomethane was nitrated [46c] with N20 S in dichloromethane at
-30°C to yield dinitrodiazomethane (III) and a nitromethyl nitrate ester (IV)
III IV
III is an explosive substance with m.p. 65°C (with decomposition).
N2 0 S possesses marked oxidizing properties [47]: a small yield of CO2 was
formed by acting with N2 0 s on CO. Baryshnikovaand Titov [123] have found
an interesting reaction of N2 Os on aromatic compounds which consists in both

57. NlTRATION AND NITRATING AGENTS 31
nitration and oxidation. Thus ch1orobenzene was transfonned into ch1oronitro-
phenols.
Dinitrogen Tetroxide and Nitrogen Dioxide (Vol. I, p. 90)
The increasing importance of dinitrogen tetroxide brought to light a number
of new facts on the properties of the substance.
Some physical constants are [1] :
freezing point -11.2°C
b.p.21.15°C
density 1.470-1.515 gJcm3
between +I0° and _10°C
viscosity 0.468-0.599 cP between +10° and -10°C
dielectric constant 2.42
surface tension 26.5 dyn/cm at 20°C
specific conductivity 10-12 ohm-1 cm-1
•
An extensive review of the properties of dinitrogen tetroxide has been given
by Riebsomer [47]. The addition of N2 04 to olefms was reviewed by Shechter
[48] and free radical reactions of N02 by Sosnovsky [48a].
The N- N bond in dinitrogen tetroxide can readily be split above room
temperature. The case of breaking N-N bond is due to its low enthalpy:
-Ml of N-N in N2 0 4 is 14.6 kcal/mol and sirnilarly in N2 0 3 is 10.2 kca1/
mol. [49].
The N- N bond is mainly 0 in nature, not of pure fr character according to
Green and Unnett [50]. This was based on a calculation by LCAO MO method
and was contradictory to earlier views. The bond N- N seems to be of an un-
usual kind, not fully understood, as the two N02 units do not rotate with res-
pect to each other in spite of the length of the bond.
The views of Green and Unnett were subjected to criticism by R. D. Brown
and Harcourt [113]. The latter pointed out that Green and Unnett had over-
looked the significant effect of a-electron delocalization upon N- N and N-C
bonds. Brown and Harcourt proposed a new electronic structure with '0 + fr'
model.
A review recently appeared [126] on the spectrum of N02 in gas phase.
The spectrum is rich and complex and was examined by modern techniques. The
study is outside the scope of the present book.
N2 0 4 is miscible with many organic liquids and is a solvent of many solid
organic substances.
Ammonium nitrate is insoluble in N2 04 but alkylarnmonium nitrates dissolve
readily [l].
Nitrogen dioxide at high temperature (ca. 620°C) was subjected to homo-
lytic dissociation into nitric oxide and oxygen atom. The same occurred upon
irradiation with 313 and 316 nrn light [51,52].

58. 32 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
The heterolytic dissociation can be represented in two ways:
(16)
(17)
and there is also an irreversible heterolytic oxygen exchange:
(18)
However the species NOt and NO;- have not been identified as free ions in
liquid N20 4, They exist as the ion pair [NOt NO;-] . In the presence of an elec-
tron-pair acceptor, complexes are formed which contain the nitronium ion.
This happens in the presence of Lewis acid halides used for the fust time (AlCI3 )
by Schaarschrnid (Vol. I, p. 103). Boron trifluoride reacts with N20 4 to form
N20 4.BF3 [53,54] and N20 4.2BF3 • Their structures were suggested as being
NOt BF3 NO;- and NOt [N{OBF3 )2] - respectively. These complexes possess
only a moderate nitrating ability. a fact which cuts some doubt on whether they
possess the structure with nitronium ion. It is known that N20 4 in nitric acid is
almost fully ionized into NO+ and NO;-. In view of the absence of NOt the
complex N20 4 .BF3 may have the structure ofanitrosoniumsalt NO+ BF3 NO;-.
Indeed it shows an ability to nitrosate and to diazotize [53] and spectroscopic
examination [56] showed only a relatively weak band at 1400 cm-1
and a strong
one at ca. 2340 cm-I
•
It is suggested [40] that an equilibrium exists between nitronium and nitros-
onium forms of the complex N20 4.BF3 i.e.
(19)
A solution N20 4 + HF should be considered as a potential nitrating agent
[57] .
Dinitrogen tetroxide can give additional complexes with compounds possess-
ing an ether bond. They were examined by Shechter et al. and described in his
review paper [48].
Here are the most important of the compounds:
1. 2(C2 HshO' N2 04
2.2(CsHIOO)·N204
(Tetrahydropyren)
3. C4 HsO' N2 04
2C4 HsO' N2 0 4
(Tetrahydrofurane)
4. 0{CH2CH2)2 0 . N20 4
m.p. -74.8°C
m.p. -56.8°C
m.p. -20.5°C
m.p. (indefmite)